Polishing compositions and methods of use thereof
This disclosure relates to a polishing composition that includes an abrasive, at least two pH adjusters, a barrier film removal rate enhancer, a low-k removal rate inhibitor; and an azole-containing corrosion inhibitor. This disclosure also features a method of using the polishing composition to polish a substrate containing copper and silicon oxide.
1 . A polishing composition, comprising:
an abrasive;
at least two pH adjusters comprising at least one inorganic base and at least one organic base, wherein the molar ratio of the at least one organic base to the at least one inorganic base is from about 0.05 to about 2;
a barrier film removal rate enhancer;
a low-k removal rate inhibitor; and
an azole-containing corrosion inhibitor.
2 . The polishing composition of claim 1 , wherein the abrasive is selected from the group consisting of alumina, silica, titania, ceria, zirconia, co-formed products of alumina, silica, titania, ceria, or zirconia, coated abrasives, surface modified abrasives, and mixtures thereof.
3 . The polishing composition of claim 1 , wherein the abrasive is in an amount of from about 0.1% to about 50% by weight of the composition.
4 . The polishing composition of claim 1 , wherein the molar ratio of the at least one organic base to the at least one inorganic base is from about 0.5 to about 2.
5 . The polishing composition of claim 1 , wherein the at least one inorganic base comprises a base selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, and any combinations thereof.
6 . The polishing composition of claim 1 , wherein the at least one organic base comprises a quaternary ammonium hydroxide, a quaternary phosphonium hydroxide, or a guanidine compound.
7 . The polishing composition of claim 6 , wherein the quaternary ammonium hydroxide or quaternary phosphonium hydroxide is selected from the group consisting of tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, diethyldimethylammonium hydroxide, dimethyldipropylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetrapentylphosphonium hydroxide, triethyl-methyl-phosphonium hydroxide, tetrakis(hydroxymethyl)phosphonium hydroxide, tetraphenylphosphonium hydroxide, and any combination thereof.
8 . The polishing composition of claim 6 , wherein the quaternary ammonium hydroxide or quaternary phosphonium hydroxide does not include covalently bound hydroxyl groups.
9 . The polishing composition of claim 1 , wherein the combined amount of the pH adjusters is in an amount of from about 0.05% to about 10% by weight of the composition.
10 . The polishing composition of claim 1 , wherein the barrier film removal rate enhancer is an organic acid or a salt thereof selected from the group consisting of gluconic acid, lactic acid, citric acid, tartaric acid, malic acid, glycolic acid, malonic acid, formic acid, oxalic acid, acetic acid, propionic acid, peracetic acid, succinic acid, potassium acetate, potassium citrate, amino acetic acid, phenoxyacetic acid, bicine, diglycolic acid, glyceric acid, tricine, alanine, histidine, valine, isoleucine, leucine, methionine, phenylalanine, cysteine, selenocysteine, glycine, proline, serine, threonine, asparagine, glutamine, aspartic acid, glutamic acid, arginine, histidine, lysine, tyrosine, tryptophan, benzoic acid, 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine O-sulfonic acid, methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholesulfonic acid, p-toluenesulfonic acid, trifluoromethane-sulfonic acid, ethyl phosphoric acid, cyanoethyl phosphoric acid, phenyl phosphoric acid, vinyl phosphoric acid, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrilotri(methylphosphonic acid), diethylenetriaminepentakis (methylphosphonic acid), N,N,N′,N′-ethylenediaminetetrakis(methylene phosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, ethylenediaminetetracetic acid, iminodiacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, nitrilotriacetic acid, diethylenetriaminepentacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraaminehexaacetic acid, diaminocycloheanetetraacetic acid, nitrilotrimethylphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), 1-hydroxyl ethylidene-1,1,-diphosphonic acid, diethylenetriamine penta (methylene phosphonic acid), salts thereof, and mixtures thereof.
11 . The polishing composition of claim 1 , wherein the barrier film removal rate enhancer is in an amount of from about 0.02% to about 4% by weight of the composition.
12 . The polishing composition of claim 1 , wherein the low-k removal rate inhibitor is a nonionic surfactant.
13 . The polishing composition of claim 12 , where the nonionic surfactant is selected from the group consisting of alcohol alkoxylates, alkylphenol alkoxylates, tristyrylphenol alkoxylates, sorbitan ester alkoxylates, polyalkoxylates, polyalkylene oxide block copolymers, alkoxylated diamines, and mixtures thereof.
14 . The polishing composition of claim 1 , wherein the low-k removal rate inhibitor is in an amount of from about 0.005% to about 5% by weight of the composition.
15 . The polishing composition of claim 1 , wherein the azole-containing corrosion inhibitor is selected from the group consisting of triazole, tetrazole, benzotriazole, tolyltriazole, methyl benzotriazole, ethyl benzotriazole, propyl benzotriazole, butyl benzotriazole, pentyl benzotriazole, hexyl benzotriazole, dimethyl benzotriazole, chloro benzotriazole, dichloro benzotriazole, chloromethyl benzotriazole, chloroethyl benzotriazole, phenyl benzotriazole, benzyl benzotriazole, aminotriazole, aminobenzimidazole, pyrazole, imidazole, aminotetrazole, adenine, xanthine, guanine, benzimidazole, thiabendazole, 1-hydroxybenzotriazole, 2-methylbenzothiazole, 2-aminobenzimidazole, 2-amino-5-ethyl-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and mixtures thereof.
16 . The polishing composition of claim 1 , wherein the azole-containing corrosion inhibitor is in an amount of from about 0.0001% to about 1% by weight of the composition.
17 . The polishing composition of claim 1 , wherein the pH of the composition is from about 7 to about 14.
18 . The polishing composition of claim 1 , wherein the at least one organic base comprises a first organic base and a second organic base different from the first organic base.
19 . The polishing composition of claim 18 , wherein the first organic base is an quaternary ammonium hydroxide or a quaternary phosphonium hydroxide and the second organic base is selected from the group consisting of alkylamines, aminoalcohols, guanidines, cyclic amines, and mixtures thereof.
20 . The polishing composition of claim 1 , further comprising at least one anionic polymer.
21 . The polishing composition of claim 20 , wherein the at least one anionic polymer is formed from one or more monomers selected from the group consisting of (meth)acrylic acid, maleic acid, acrylic acid, acrylamide, malic acid, methacrylic acid, vinyl phosphonic acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, acrylamide, acrylamidopropyl sulfonic acid, phosphonic acid, phosphoric acid, vinyl phosphoric acid, butadiene/maleic acid, caprolactam, etherimide, 2-ethyl-2-oxazoline, N-iso-propylacrylamide, sodium phosphinite and co-formed products thereof, and sodium, potassium and ammonium salts thereof.
22 . The composition of claim 20 , wherein the at least one anionic polymer comprises poly(4-styrenylsulfonic) acid (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) terpolymer, phosphinocarboxylic acid, hydrolyzed polymaleic anhydride, or a mixture thereof.
23 . The composition of claim 20 , wherein the at least one anionic polymer is in an amount of from about 0.00001% to about 50% by weight of the cleaning composition.
24 . A method of polishing a substrate, comprising the steps of:
applying the polishing composition of claim 1 to a surface of a substrate, wherein the surface comprises copper and silicon oxide; and
bringing a pad into contact with the surface of the substrate and moving the pad in relation to the substrate.